Novel cyclopropane carboxylates

ABSTRACT

Novel 2,2-dimethyl-cyclopropane carboxylic acid derivatives of the formula ##STR1## wherein X 1  and X 2  are individually halogen, R 1  is selected from the group consisting of halogen, alkyl of 1 to 8 carbon atoms, optionally substituted aryl of 6 to 14 carbon atoms, perfluoroalkyl of 1 to 8 carbon atoms, --CN and ##STR2## R&#39; is alkyl of 1 to 8 carbon atoms, Y is selected from the group consisting of ##STR3## Alk 1  is optionally unsaturated alkyl of 1 to 8 carbon atoms no substituted or substituted with at least one functional group, Ar is aryl of 6 to 14 carbon atoms no substituted or substituted with at least one functional group, Alk 2  and Alk 3  and Alk 2  &#39; and Alk 3  &#39; are optionally unsaturated alkyl of 1 to 8 carbon atoms no substituted or substituted with at least one functional group or together with ##STR4## form the rings ##STR5## wherein A is optionally unsaturated alkyl of 1 to 6 carbon atoms optionally substituted with at least one functional group, R&#34; is alkyl of 1 to 6 carbon atoms no substituted or substituted with at least one functional group or aryl of 6 to 14 carbon atoms no substituted or substituted with at least one functional group and R is selected from the group consisting of hydrogen, alkyl of 1 to 8 carbon atoms and residue of an alcohol used in pyrethrinoid esters having pestioidal activity.

This is a division of Ser. No. 123,374 filed Nov. 20, 1987 now U.S. Pat.No. 4,925,874.

STATE OF THE ART

Relevant prior art includes Chem. Abstract, Vol. 86, 139480a,Tetrahedron Letters, Vol. 27, No. 19, p. 2135 to 2138 and 2139 to 2142,European Patent No. 21,521, European Application 187,674 and GermanPatent Application Nr. 2,639,777 and British Patent Application Nr.2,099,810.

OBJECTS OF THE INVENTION

It is an object of the invention to provide the novel compounds offormula I and a process for their preparation.

It is another object of the invention to provide novel pesticidalcompositions and a novel method of combatting pests.

These and other objects and advantages of the invention will becomeobvious from the following detailed description.

THE INVENTION

The novel compounds of the invention are compounds of the formula##STR6## wherein X₁ and X₂ are individually halogen, R₁ is selected fromthe group consisting of halogen, alkyl of 1 to 8 carbon atoms,optionally substituted aryl of 6 to 14 carbon atoms, perfluoroalkyl of 1to 8 carbon atoms, --CN and ##STR7## R' is alkyl of 1 to 8 carbon atoms,Y is selected from the group consisting of ##STR8## Alk₁ is optionallyunsaturated alkyl of 1 to 8 carbon atoms no substituted or substitutedwith at least one functional group, Ar is aryl of 6 to 14 carbon atomsno substituted or substituted with at least one functional group, Alk₂and Alk₃ and Alk₂ ' and Alk₃ ' are optionally unsaturated alkyl of 1 to8 carbon atoms no substituted or substituted with at least onefunctional group or together with ##STR9## form the rings ##STR10##wherein A is optionally unsaturated alkyl of 1 to 6 carbon atomsoptionally substituted with at least one functional group, R" is alkylof 1 to 6 carbon atoms no substituted or substituted with at least onefunctional group or aryl of 6 to 14 carbon atoms no substituted orsubstituted with at least one functional group and R is selected fromthe group consisting of hydrogen, alkyl of 1 to 8 carbon atoms andresidue of an alcohol used in pyrethrinoid esters.

The compounds of formula I have several centers of asymmetry, thecarbons in positions 1 and 3 of cyclopropane and the carbons inpositions 1' and 2' of the lateral chain ##STR11## can also presentseveral centers of asymmetry in part R. The subject of the invention isthe various possible stereoisomers as well as mixtures of thesestereoisomers.

Examples of X₁ and X₂ are chlorine, bromine and iodine and examples ofR₁ are halogen such as bromine, chlorine or fluorine, alkyl such asmethyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl and tertbuty, arylsuch as phenyl, substituted aryl such as phenyl substituted with ahalogen such as chlorine, perfluoroalkyl such as trifluoromethyl and##STR12## where R' is methyl, ethyl, n-propyl, isopropyl, tert.-butyl orhexafluoroisopropyl.

Examples of preferred groups of X₁, X and R₁ are ##STR13##

Alk₁, Alk₂, Alk₃, Alk₂ ' and Alk₃ ' preferably are methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl or t-butyl Ar preferably isphenyl

When Alk₁, Alk₂, Alk₃, Alk₂ ', Alk₃ ' and Ar are substituted, thesubstituent is preferably at least one of halogen, --CF₃, hydroxyl,carboxyl amino, and ammonium, alkyl and alkoxy of 1 to 4 carbon atomssuch as methyl and methoxy.

Examples of R" are methyl, ethyl, propyl, phenyl, each optionallysubstituted with halogen.

A preferably is a saturated carbonated chain of 1 to 4 carbon atoms,optionally substituted by at least one member selected from the groupconsisting of alkyl of 1 to 5 carbon atoms, halogen, --CF₃ or hydroxy.When R is alkyl, it is preferably methyl, ethyl, n-propyl, isopropyl,but isobutyl or tert-butyl.

The preferred values of the alcohols used in the synthesis ofpyrethrinoid esters will be indicated hereafter.

Among the preferred compounds of formula I are those wherein X₁ and X₂are bromine, those wherein R₁ is bromine, chlorine or fluorine and thosewherein R₁ is --CF₃. Other preferred compounds of formula I are thosewherein Y is --SO₂ Alk₁ and Alk₁ is alkyl or alkenyl of up to 8 carbonatoms, for example SO₂ CH₃, those wherein Y is SO₂ Ar, Ar having thesame significance as previously, as well as compounds of formula I inwhich R is hydrogen, or optionally substituted alkyl of 1 to 8 carbonatoms, or benzyl optionally substituted by a member chosen from thegroup constituted of alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 6carbon atoms, alkenyloxy of 2 to 6 carbon atoms, alkadienyl of 4 to 8carbon atoms, methylenedioxy and halogen, or ##STR14## in which R'" ishydrogen or methyl and R₂ is a monocyclic aryl or a --CH₂ ═CH group andparticularly 5-benzyl-3-furyl methyl, or ##STR15## in which a ishydrogen or methyl and R₃ is aliphatic organic radical of 2 to 6 carbonatoms and containing at least one carbon-carbon unsaturation andparticularly one of the following --CH₂ --CH═CH₂, --CH₂ --CH═CH--CH₃,--CH₂ --CH═CH--CH═CH₂, --CH₂ --CH═CH--CH₂ --CH₃, --CH₂ --C═CH, or##STR16## in which a is hydrogen or methyl, R₃ has the above definition,R₁ ' and R₂ ' are individually hydrogen, halogen, alkyl of 1 to 6 carbonatoms, aryl of 6 to 10 carbon atoms, alkyloxycarbonyl of 2 to 5 carbonatoms, or cyano or ##STR17## in which B' is oxygen or sulfur, ##STR18##or --CH₂ -- or a sulfoxide or a sulfone and R₄ is hydrogen, --C═N,methyl, --CONH₂, --CSNH₂, or --C═CH, R₅ is halogen or methyl and n is anumber equal to 0, 1 or 2, and particularly one of the following groups:3-phenoxy-benzyl, α-cyano-3-phenoxy-benzyl α-ethynyl-3-phenoxy-benzyl,3-benzoyl-benzyl, 1-(3-phenoxy-phenyl)-ethyl orα-thioamido-3-phenoxy-benzyl, or ##STR19## in which the substituents R₆,R₇, R₈ and R₉ are hydrogen, chlorine, or methyl and in which S/Isymbolizes an aromatic ring or a similar dihydro or tetrahydro ring, or##STR20## in which R₁₀ is hydrogen or --CN, R₁₂ is --CH₂ -- or oxygen,R₁₁ is thiazolyl or thiadiazolyl of which the bond with ##STR21## can befound at any one of the available positions, R₁₂ being linked to R₁₁ bythe carbon atom included between the sulfur atom and a nitrogen atom, or##STR22## in which R₁₃ is hydrogen or --CN, or ##STR23## in which R₁₃ isdefined as above, and benzoyl is in position 3 or 4, or ##STR24## inwhich R₁₄ is hydrogen, methyl, ethynyl or cyano and R₁₅ and R₁₆, beingdifferent, is hydrogen, fluorine or bromine, or ##STR25## in which R₁₄is defined as above, each R₁₇ is independently alkyl of 1 to 4 carbonatoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms,alkylsulfonyl of 1 to 4 carbon atoms, trifluoromethyl,3,4-methylenedioxy, chloro, fluoro or bromo, p is a number equal to 0, 1or 2 and B" is oxygen or sulfur, or ##STR26## in which R₁₈ is hydrogen,methyl, ethynyl, or cyano and R₁₉, being different, is hydrogen,fluorine or bromine and Ar is aryl of 6 to 14 carbon atoms, or ##STR27##

Among the preferred compounds of formula I are compounds in which R isone of the following: ##STR28##

Among the preferred compounds of formula I: α-cyano-3-phenoxy-benzyl1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-(methylsulfonyloxyethyl)-2,2,2-tribromoethyl]-cyclopropanecarboxylate α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, [2-methyl-3-phenyl-benzyl] 1R-[1α, 3α-(RS,RS)]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate and α-cyano-3-phenoxy-benzyl 1R-[1α-, 3α-(RS*,RS*)]2,2-dimethyl-3-[2trifluoromethyl-2-bromo-2-chloro-1-methysulfonyloxyethyl]-cyclopropanecarboxylate.

The novel process of the invention for the preparation of the compoundsof formula I comprises reacting a compound of the formula ##STR29##wherein R has the above definitions with a compound of the formula##STR30## wherein R₁, X₁ and X₂ have the above definitions in thepresence of a base to obtain a compound of the formula ##STR31##submitting the latter to the action of a sulfonylation, phosphonylation,thiophosphorylation or acylation agent to obtain a compound of theformula ##STR32## which is optionally changed into the correspondingacid which is optionally reacted with an esterification agent to obtainanother compound of formula I.

In a preferred method of the process of the invention, the base used forreaction of the compound of formula II with the compound of formula V ispreferably selected from the group consisting of alkali metalalcoholates, alkali metal hydrides and alkali metal hydroxides,preferably potassium hydroxide, potassium methylate or potassiumtertbutylate.

The sulfonylation agent may have the formula ##STR33## with Z beinghalogen, O--PO₃ -Alk-OSO₂ Alk or imidazolyl and Alk is alkyl of 1 to 8carbon atoms, the phosphorylation agent may have the formula ##STR34##with Z being halogen, --OSO₂ R or imidazolyl X is oxygen or sulfur andAlk₂ and Alk₃ have the above definitions and the acylation agent mayhave the formula ##STR35## with Z being --OCOAlk, halogen, ##STR36## orimidazolyl.

The agent of formula I can be prepared by reacting an ester of formula Iwith an acid hydrolysis agent, for example p-toluenesulfonic acid,sulfuric acid or acetic acid and the esterification agent is an alcoholwith esterification being carried out according to standard method

The products of formula IV obtained by the process are new products withthe exception of products for which X₁, X₂ and R₁ each is halogen.

The novel pesticidal compositions of the invention are comprised of apesticidally effective amount of at least one stereoisomer or mixturesthereof of formula I and an inert carrier. The compositions are usefulfor combatting vegetation parasites, premises parasites and warm-bloodedanimal parasites and are useful particularly to combat insects,nematodes and vegetation and animal acariens.

In compositions intended for agricultural use and for use in premises,the active compounds of formula I may have added to them one or moreother pesticide agents and these compositions may be in the form ofpowders, granules, suspensions, emulsions, solutions, solutions foraerosol combustible strips, baits or other preparations normallyemployed for the utilization of this type of compound.

In addition to the active principle, the compositions generally containa vehicle and/or a non-ionic surface active agent to ensure a uniformdispersion of the substances which form the mixture. The vehicleutilized can be a liquid such as water, alcohol, hydrocarbons or otherorganic solvents, a mineral, animal or vegetable oil, a powder such astalc clays, silicates, kieselguhr or a combustible solid.

The products of formula I can be used particularly to combat insects inthe agricultural field, to combat, for example, aphids, larvae oflepidoptera and coleoptera. They are used at doses between 10 g and 300g of active material per hectare. The products of formula I can also beused to combat premises insects, to combat particularly flies,mosquitoes and cockroaches. The products of formula I may also be usedto combat parasitic insects of animals, for example, lice, particularlyon cattle, sheep and fowls.

The invention also has particularly as its object insecticidecompositions containing as active principle at least one of thecompounds previously defined. The preferred insecticidal compositionscontain as active principle α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-(methylsulfonyloxyethyl)-2,2,2-tribromoethyl]-cyclopropanecarboxylate α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, [2-methyl-3-phenyl-benzyl] 1R-[1α,3α-(RS,RS)]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate and α-cyano-3-phenoxy-benzyl 1R-[1α-, 3α-(RS*,RS*)]2,2-dimethyl-3-[2trifluoromethyl-2-bromo-2-chloro-1-methysulfonyloxyethyl]-cyclopropanecarboxylate. The insecticidal compositions of the invention preferablycontain from 0.005% to 10 % by weight of active material.

According to an advantageous way of operating, for use in premises theinsecticide compositions of the invention are utilized in the form offumigating compositions. The insecticide compositions of the inventionmay then be constituted advantageously, for the non-active part, of acombustible serpentine or of an incombustible fibrous substrate. In thislatter case, the fumigant obtained after incorporation of the activematerial is placed on a heating apparatus such as an electroemanator. Ifan insecticide serpentine is used, the inert support can be, forexample, composed of pyrethrum marc, Tabu powder (or Machilus Thunbergiileaf powder), pyrethrum stem powder, cedar leaf powder, wood powder(such as pine sawdust), starch and coconut shell powder. The quantity ofactive material can then be, for example, from 0.03 to 1% by weight. Ifan incombustible fibrous support is used, the quantity of activematerial can then be, for example, from 0.03 to 95% by weight.

The compositions of the invention for use in premises can also beobtained by preparing an atomizable oil based on the active principle,this oil soaking the wick of a lamp and then being submitted tocombustion. The concentration of active principle incorporated in theoil is preferably from 0.03 to 95% by weight.

The invention compounds can also be used to combat parasitic acariens ofvegetation and the biological study further on clearly shows theremarkable acaricide properties of the products. The compositions mayalso be used to combat parasitic nematodes of vegetation. Therefore, theinvention also has as its object acaricide compositions as well asnematocide compositions containing as active principle at least onecompound of formula I. The acaricide and nematocide compositions can bepresented in particular in the form of powders, granules, suspensions,emulsions, and solutions.

For acaricide use, it is preferred to use wettable powders for foliaratomization containing from 1 to 80% of active principle, or liquids forfoliar atomization containing from 1 to 500 g/l of active material.Powders for foliar powdering can also be used containing from 0.05 to 3%of active material. For nematocide use, it is preferred to use liquidsfor soil treatment containing from 300 to 500 g/l of active principle.The acaricide and nematocide compounds of the invention are usedpreferably at quantities between 1 and 100 g of active material perhectare.

The compounds of formula I can also be used to combat parasitic acariensof animals such as ticks and particularly ticks of the Boophilusspecies, those of the Hyalomnia species, those of the Amblyomnia speciesand those of the Rhipicephalus species, or to combat all sorts of mitesand particularly sarcoptic mites, psoroptic mites and chorioptic mites.Therefore, the invention also has as its subject compositions used incombatting parasitic acariens of warm-blooded animals, characterized inthat they contain at least one product defined above.

Those compositions can be administered externally by vaporizing, byshampooing, by bath, or by painting on. They can also be administered bypainting on the backbone by the so-called "pour on" method and they canalso be administered by the digestive route.

When it is a matter of combatting parasitic acariens of animals, thecompositions are very often incorporated in alimentary compositions inassociation with a nutritive mixture suitable for feeding the animalwhich nutritive mixture vary according to the animal species. It cancontain cereals, sugars and seeds, soya, ground-nut and sunflower cakes,meals of animal origin, for example, fish meals, synthetic amino acids,mineral salts, vitamins and anti-oxidants. Thus, the invention also hasas its object compositions intended for animal feeding containing asactive principle at least one of the products of formula I.

To increase the biological activity of the products of the invention,they can have added to them standard synergists used in similar casessuch as 1-(2,5,8-trioxadodecyl)-2-propyl-4,5-methylenedioxy benzene (orpiperonyl butoxide) orN-(2-ethylheptyl)-bicyclo[2,2,1]-5-hepten-2,3-dicarboximide, orpiperonyl-bis-2-(2'n-butoxyethoxy)-ethyl-acetal (or tropital).

The invention also has as its object compositions endowed withinsecticide, acaricide or nematocide activity characterized in that theycontain as active material, on the one hand, at least one of thecompounds of formula I, and on the other hand, at least one of thepyrethrinoid esters selected from the group consisting of esters ofallethrolones, of 3,4,5,6-tetrahydrophthalimidomethyl alcohol, of5-benzyl-3-furyl methyl alcohol, of 3-phenoxy-benzyl alcohol andα-cyano-3-phenoxy-benzyl alcohols with chrysanthemic acids, by theesters of 5-benzyl-3-furyl methyl alcohol with2,2-dimethyl-3-(2-oxo-3-tetrahydrothiophenylidenemethyl)-cyclopropane-1-carboxylicacids, by the esters of 3-phenoxy-benzyl alcohol andα-cyano-3-phenoxy-benzyl alcohols with2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acids, bythe esters of α-cyano-3-phenoxy-benzyl alcohols with2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-1-carboxylic acids, bythe esters of 3-phenoxy-benzyl alcohol with2-parachlorophenyl-2-isopropyl acetic acids, by the esters ofallethrolone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, of5-benzyl-3-furyl-methyl alcohol, of 3-phenoxy-benzyl alcohol andα-cyano-3-phenoxy-benzyl alcohols with2,2-dimethyl-3-(1,2,2,2-tetrahaloethyl)-cyclopropane-1-carboxylic acids,in which "halo" represents a fluorine, chlorine or bromine atom, itbeing understood that the compounds I can exist in all their possiblestereoisomeric forms, as can the acid and alcohol moiety of the abovepyrethrinoid esters. The said compositions are of particular interestbecause of their wider range of parasitic activity due to thepolyvalency of their action and having a synergistic effect in someinstances.

The compounds of formula I may also be used to prepare a compound of theformula ##STR37## by reacting a compound of formula I with a reducingagent. The preferred reducing agent is hydrogen in the presence of ahydrogenation catalyst such as palladium but reduction can also beeffected with zinc in the presence of an acid or with copper-zinc in thepresence of an alcohol or any other conventional method for simultaneousremoval of a halogen and --OY.

The preferred compounds of formula III which may be produced by theabove process starting from the corresponding compounds of formula Ihave the formulae ##STR38##

In the following examples there are described several preferredembodiments to illustrate the invention. However, it should beunderstood that the invention is not intended to be limited to thespecific embodiments.

EXAMPLE 1 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-(1-hydroxy-2,2,2-tribromoethyl)-cyclopropane carboxylateSTEP A

1R-[1α,3α-(R)] 2,2-dimethyl-3-[1-trimethylsilyloxy)2,2,2-tribromoethyl]-cyclopropane carboxylic acid

18.5 g of potassium tertbutylate, 40 ml of tetrahydrofuran and 80 ml oftertbutyl alcohol were introduced at -60° C. over 30 minutes into asolution containing 30.25 g of 1R-[1α,-3α-(R)]2,2-dimethyl-3-[1-hydroxy-2,2,2-tribromoethyl]-cyclopropane carboxylicacid [described in French Patent No. 2,396,006] and 300 ml oftetrahydrofuran. The mixture was stirred for 10 minutes at -60° C. and80 ml of trimethylsilyl chloride and 60 ml of tetrahydrofuran wereintroduced dropwise. The mixture was stirred for 10 minutes at -60° C.and the ambient temperature was allowed to rise to -20° C. Then,stirring was carried out for half an hour at -20° C. and the reactionmixture was poured into a saturated solution of sodium bicarbonate.Extraction was carried out with chloroform and the extract were driedand evaporated to dryness under reduced pressure. 100 ml of water with1% of acetic acid were added and the mixture was stirred for 15 minutes.The product obtained was separated, dissolved in chloroform, dried andevaporated to dryness under reduced pressure to obtain 16 g of1R-[1α,3α-(R)] 2,2-dimethyl-3-[1-trimethylsilyloxy)2,2,2-tribromoethyl]-cyclopropane carboxylic acid melting at 147° C.

STEP B

α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-trimethylsilyloxy)-2,2,2-tribromoethyl]-cyclopropanecarboxylate

A solution of 14 g of dicyclohexylcarbodiimide and 140 ml of methylenechloride were introduced into a solution of 32 g of the product of StepA, 300 ml of methylene chloride and 15 g of (S)α-cyano-3-phenoxybenzylalcohol. The mixture was stirred for 3 hours at 20° C. to 25° C., thenseparated and evaporated to dryness under reduced pressure. Purificationwas carried out by chromatography, elution with a hexane-isopropyl ethermixture (8-2) to obtain 34 g of α-cyano-3-phenoxy-benzyl 1R-[1α-(S)3α-(R)]2,2-dimethyl-3-[1-trimethylsilyloxy)-2,2,2-tribromoethyl]-cyclopropanecarboxylate melting at 98° C.

STEP C

α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-(1-hydroxy-2,2,2-tribromoethyl)-cyclopropane carboxylate

3 ml of 2N hydrochloric acid were added to a solution of 8 g of theproduct of Step B and 150 ml of methanol and after stirring for 30minutes at 20° C. to 25° C., the methanol was expelled. The remainderwas taken up in methylene chloride, dried and evaporated to drynessunder reduced pressure. The residue was chromatographed over a mediumeluting with a hexane-ethyl acetate mixture (7-3) to obtain 6.5 g ofα-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-trimethylsiloxyl)-2,2,2-tribromoethyl]-cyclopropanecarboxylate. ##STR39##

EXAMPLE 2 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-(methylsulfonyloxyethyl)-2,2,2-tribromoethyl]-cyclopropanecarboxylate

0.91 ml of triethylamine were introduced at 0° to 5° C. into a mixtureof 3 g of the product of Example 1, 30 ml of tetrahydrofuran and 0.5 mlof mesyl chloride and the mixture was stirred for 2 hours at 0° to 5° C.0.5 ml of mesyl chloride and 0.91 ml of triethylamine were added againand the precipitate formed was separated. The organic phase was washedwith water, dried and evaporated to dryness under reduced pressure.Chromatography was done on silica and elution with a hexane-ethylacetate mixture (7-3) yielded 2.6 g of α-cyano-3-phenoxy-benzyl1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-(methylsulfonyloxy)-2,2,2-tribromoethyl]-cyclopropanecarboxylate. ##STR40##

EXAMPLE 3 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S*) 3α-(R*)]2,2-dimethyl-3-(2,2,2-tribromo-1-ethyl-sulfonyloxyethyl)-cyclopropanecarboxylate

Using the procedure of Example 2, the product of Example 1 and ethanesulfonyl chloride were reacted to obtain α-cyano-3-phenoxy-benzyl1R-[1α-(S*) 3α-(R*)]2,2-dimethyl-3-(2,2,2-tribromo-1-ethyl-sulfonyloxyethyl)-cyclopropanecarboxylate melting at 133° C. and having a specific rotation of [α]_(D)²⁰ =+43° (c=1% in CHCl₃).

EXAMPLE 4 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-isopropylsulfonyloxy-ethyl]-2,2-dimethyl-cyclopropane carboxylate

0.35 ml of triethylamine were introduced at a temperature of 0° to 5° C.into a solution of 1.5 g of the product of Example 1, 15 ml oftetrahydrofuran and 0.32 g of isopropylsulfonyl chloride and the mixturewas stirred at 0° to 5° C. for 30 minutes. The reaction mixture waspoured into an aqueous solution of hydrochloric acid at pH 5 and thenwas extracted with methylene chloride. The extracts were dried, filteredand evaporated to dryness. 1.5 g of p-nitroperbenzoic acid wereintroduced and the mixture was stirred for 30 minutes at 20° to 25° C.and evaporated to dryness to obtain 3.2 g of crude product which waschromatographed over silica and eluted with a hexane-acetic acid (8-2)mixture to obtain 1.43 g of α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-isopropylsulfonyloxy-ethyl]-2,2-dimethyl-cyclopropane carboxylate with a specificrotation of [α]_(D) ²⁰ =+42°±1.5 (c=0.7% in CHCl₃).

EXAMPLE 5 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2,-tribromo-1-(2-methyl-2-propene-1-sulfonyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate

Using the procedure of Example 2, the product of Example 1 and(1-sulfonyloxy-2-methyl)-2-propenyl chloride were reacted to obtainα-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-(2-methyl-2-propene-1-sulfonyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate melting at 107° C.

EXAMPLE 6 α-(R,S) cyano 1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-(R,S)3α-(R)]2,2-dimethyl)-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate STEP A: α-(R,S) cyano 1-(6-phenoxy-2-pyridyl)-methyl1R-[1α-(R,S) cyano 1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-(R,S) 3α-(R*)]2,2-dimethyl-3-[2,2,2-tribromo-1-trimethylsilyloxyethyl]-cyclopropanecarboxylate

Using the procedure of Step B of Example 1, 1R-[1α-, 3α-(R)]2,2-dimethyl-3-[trimethylsilyloxy-2,2,2-tribromoethyl]-cyclopropanecarboxylic acid and α-(R,S) cyano 1-(6-phenoxy-2-pyridyl)-methyl alcoholwere reacted to obtain α-(R,S) cyano 1-(6-phenoxy-2-pyridyl)-methyl1R-[1-α(R,S) cyano 1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-α(R,S) 3α-(R*)]2,2-dimethyl-3-[2,2,2-tribromo-1-trimethylsilyloxyethyl]-cyclopropanecarboxylate melting at 160° C.

STEP B: α-(R,S) cyano-1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-(R,S)3α-(R*)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

Using the procedure of Example 1, the product of Step A was reacted toobtain α-(R,S) cyano-1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-(R,S)3α-(R*)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate which was used as is in the next step.

STEP C: α-(R,S) cyano 1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-(R,S)3α-(R*)] 2,2-dimethyl3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropane carboxylate

Using the procedure of Example 2, the product of Step B and mesylchloride were reacted to obtain α-(R,S) cyano1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-(R,S) 3α-(R*)] 2,2-dimethyl3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropane carboxylatewith a specific rotation of [α]_(D) ²⁰ =+6°±1.5° (c=0.3% in CHCl₃).

EXAMPLE 7 3-phenoxy-benzyl 1R-[1α-, 3α-(R)]2,2-dimethyl-3-(2,2,2-tribromo-1-methylsulfonyloxyethyl)-cyclopropanecarboxylate STEP A: 3-phenoxy-benzyl 1R-[1α-, 3α-(R)]2,2-dimethyl-3-(2,2,2-tribromo-1-trimethylsilyloxyethyl)-cyclopropanecarboxylate

Using the procedure of Example 6, the product of Step A of Example 1 andphenoxy-benzyl alcohol were reacted to obtain 3-phenoxybenzyl1R-[1α,3α(R)]2,2-dimethyl-3-(2,2,2-tribromo-1-trimethylsilyloxyethyl)-cyclopropanecarboxylate.

STEP B: 3-phenoxy-benzyl 1R-[1α-, 3α-(R*)]2,2-dimethyl-3-(2,2,2-tribromo-1-hydroxyethyl)-cyclopropane carboxylate

Using the procedure of Step B of Example 6, the product of Step A wasreacted to obtain 3-phenoxybenzyl 1R-[1α, 3α(R*)]2,2-dimethyl-3-(2,2,2-tribromo-1-hydroxyethyl)-cyclopropane carboxylatewhich was used as is in the next step.

STEP C: 3-phenoxy-benzyl 1R-[1α-, 3α-(R)]2,2-dimethyl-3-(2,2,2-dibromo-1-methylsulfonyloxyethyl)-cyclopropanecarboxylate

Using the procedure of Step C of Example 6, the product of Step B wasreacted to obtain 3-phenoxy-benzyl 1R-[1α-, 3α-(R)]2,2-dimethyl-3-(2,2,2-dibromo-1-methylsulfonyloxyethyl)-cyclopropanecarboxylate melting at 72° C.

EXAMPLE 8 (S)α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl- 3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate STEP A: α-Cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-trimethylsilyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate

Using the procedure of Example 7, 1R-[1α-, 3α-(R)]2,2-dimethyl-3-[1-trimethylsilyloxy-2,2,2-tribromoethyl]-cyclopropanecarboxylic acid and (S)α-cyano-3-phenoxy-4-fluoro-benzyl alcohol werereacted to obtain α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-trimethylsilyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate melting at 133° C.

STEP B: (S) α-Cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-hydroxyethyl]-2,2-dimethyl-cyclopropane carboxylate

Using the procedure of Example 7 by hydrolysis of the product of Step A,there was obtained (S) α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S)3α-(R)] 3-[2,2,2-tribromo-1-hydroxyethyl]-2,2-dimethyl-cyclopropanecarboxylate which was used as is in the next step.

STEP C: (S) α-Cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

Using the procedure of Example 7, the product of Step B and mesylchloride were reacted to obtain α-cyano-3-phenoxy-4-fluoro-benzyl1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate with a specific rotation of [α]_(D) ²⁰ =+34°±1° (c=1% inCHCl₃)

EXAMPLE 9 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-(2-propene-1-sulfonyloxyethyl]-cyclopropanecarboxylate

By esterifying the product of Example 1 with 1-sulfonyloxy-2-propenylchloride, there was obtained α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-(2-propene-1-sulfonyloxyethyl]-cyclopropanecarboxylate melting at 96° C.

EXAMPLE 10 (S) α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-trifluoromethylcarbonyloxyethyl]-cyclopropanecarboxylate STEP A: 1,1-dimethylethyl 1R-[1α, 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1trifluorometylcarbonyloxyethyl]-cyclopropanecarboxylate

16 ml of trifluoroacetic acid were added at 10° to 15° C. to a mixtureof 5 g of tertbutyl2,2-dimethyl-3-[2,2,2-tribromo-1-hydroxyethyl]-cyclopropane carboxylateand 20 ml of pyridine and the reaction mixture was allowed to return to20° to 25° C. and was stirred for 90 minutes. The reaction mixture waspoured into a mixture of water and ice and extraction was carried outwith ether. The extracts were dried and evaporated to dryness underreduced pressure to obtain a residue which was cooled with hexane, driedand brought to dryness to obtain 5.09 g of 1,1-dimethylethyl 1R-[1α,3α-(R)] 2,2,2-tribromo-1-trifluoromethylcarbonyloxyethyl]-cyclopropanecarboxylate melting at 102° C.

STEP B:1R-[1α,3α-(R)]-2,2-dimethyl-3-[2,2,2-tribromo-1-trifluoromethylcarbonyloxyethyl]-cyclopropanecarboxylic acid

By hydrolysing the product obtained at Step A in benzene at reflux1R-[1α,3α-(R)]-2,2-dimethyl-3-[2,2,2-tribromo-1-trifluoromethylcarbonyloxyethyl]-cyclopropanecarboxylic acid melting at 178° C., is obtained.

STEP C: (S) α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-trifluoromethylcarbonyloxyethyl]-cyclopropanecarboxylate

Using the procedure of Step B of Example 1, the acid of Step B and (S)α-cyano-3-phenoxy-benzyl alcohol were reacted to obtain (S)α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-trifluoromethylcarbonyloxyethyl]-cyclopropanecarboxylate melting at 79° C.

EXAMPLE 11 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[(1-diethoxyphosphoryloxy)-2,2,2-tribromoethyl]-cyclopropanecarboxylate STEP A: Dimethylethyl 1R-[1α-,3α-(R)]3-[2,2,2-tribromo-(diethoxyphosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate

5.05 g of bromoform, 35 g of potassium tertbutylate and 20 ml oftetrahydrofuran were added at -60° C. to a suspension of 4 g ofdimethylethyl keto [1α-, 3α-(R)]-cyclopropane carboxylate and 40 ml oftetrahydrofuran and the mixture was stirred for 15 minutes at -60° C.,3.6 g of diethoxyphosphoryloxy chloride were added and the mixture wasstirred for one hour and a half at -60° C. and poured into a normalsolution of hydrochloric acid. Extraction was carried out with ether andthe extracts were washed with water, dried and evaporated to drynessunder reduced pressure to obtain 7.09 g of dimethylethyl 1R-[1α-,3α-(R)]3-[2,2,2-tribromo-(diethoxyphosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate melting at 79° C.

STEP B: 1R-[1α-,3α-(R)]3-[2,2,2-tribromo-1-diethoxyphosphoryloxy]-2,2-dimethyl-cyclopropanecarboxylic acid

A solution of 5 g of product of Step A, 50 ml of benzene and 0.5 g ofp-toluene sulfonic acid was refluxed for one hour and the reactionmixture was cooled to 10° to 20° C. and poured into water. The organicphase was decanted, dried and evaporated to dryness under reducedpressure. The residue was taken up in hexane and the product obtainedwas separated to obtain 3 g of 1R-[1α-, 3α- -(R)]3-[2,2,2-tribromo-1-diethoxyphosphoryloxy-2,2-dimethyl-cyclopropanecarboxylic acid melting at 146° C.

STEP C: α-Cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α-(R)]2,2-dimethyl-3-[(1-diethoxyphosphoryloxy)-2,2,2-tribromoethyl]-cyclopropanecarboxylate

1.22 g of cyclohexycarbodiimide and 5 ml of methylene chloride wereadded to a mixture of 3 g of acid of Step B, 1.34 g of (S)α-cyano-3-phenoxy-benzyl alcohol, 50 mg of 4-dimethylamino-pyridine and30 ml of methylene chloride and the reaction mixture was allowed toreturn to ambient temperature and was maintained with stirring for onehour and a half. The product obtained was separated and brought todryness, then chromatographed over silica, eluting with a hexane-ethylacetate mixture (6-4) to obtain 3.3 g of α-cyano-3-phenoxy-benzyl1R-[1α- (S) 3α- (R)]2,2-dimethyl-3-[(1-diethoxyphosphoryloxy)-2,2,2-tribromoethyl]-cyclopropanecarboxylate.

EXAMPLE 12 α-Cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α-(R)]3-[2,2,2-tribromo-1-(2-oxo-1,3,2-dioxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate STEP A: 1,1-dimethylethyl 1R-[1α-, 3α-(R)]3-[2,2,2-tribromo-1-(2-oxo-1,3,2-dioxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate

4.6 ml of bromoform were added at -60° C. to a solution of 9.9 g of1,1-dimethylethyl 2,2-dimethyl-3-keto-(1R, 3α-) cyclopropane carboxylatein 100 ml of tetrahydrofuran and then 6.05 g of potassium tertbutylateand 50 ml of tetrahydrofuran were added at -60° C. Then, 7.5 g of2-oxo-1,3,2-dioxophospholane chloride and 25 ml of tetrahydrofuran wereadded over 15 minutes at -60° C. and the mixture was stirred at -60° C.for 15 minutes, then poured into an aqueous solution of hydrochloricacid. The mixture was extracted with methylene chloride and the organicphases were washed with water, dried and evaporated to dryness underreduced pressure to obtain 27 g of residue which was triturated with 100ml of ethyl ether. The product obtained was filtered and dried to obtain18.4 g of 1,1-dimethylethyl 1R-[1α-, 3 α-(R)]3-[2,2,2-tribromo-1-(2-oxo-1,3,2-dioxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate melting at 210° C.

STEP B: 1R-[1α-, 3α-(R)]3-[2,2,2-tribromo-1-(2-oxo-1,3,2-dioxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylic acid

12.9 g of the product of Step A were added at reflux to a solution of500 ml of benzene and p-tolune sulfonic acid and the mixture wasrefluxed for 30 minutes. The product obtained was brought to dryness,taken up in ethyl acetate, stirred for 15 minutes and filtered to obtain5.5 g of 1R-[1α-, 3α-(R)]3-[2,2,2-tribromo-1-2(2-oxo-1,3,2-dioxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylic acid melting at 225° C.

STEP C: (S) α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-(1-oxo-1,3,2-oxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate

Using the procedure of Example 1, Step B, 2.5 g of the product of Step Band 1.07 g of (S)α-cyano-3-phenoxy-benzyl alcohol were reacted to obtain(S)α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-tribromo-1-(2-oxo-1,3,2-oxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate melting at 155° C. and having a specific rotation of [α]_(D)²⁰ =+42°±1.5° (c=1% in CHCl₃).

EXAMPLE 13 2-Methyl-3-phenyl-benzyl 1R-[1α-, 3α-(R)]3-[2,2,2-tribromo-1-(2-oxo-1,3,2-dioxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate

The acid of Step B of Example 6 and [2-methyl-2-phenylphenyl]-methylalcohol were reacted to obtain 2-methyl-3-phenyl-benzyl 1R-[1α-, 3α-(R)]3-[2,2,2-tribromo-1-(2-oxo-1,3,2-dioxaphospholanyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate melting at 182° C.

EXAMPLE 14 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R or S)]3-[2,2,2-trichloro-1-(diethoxythiophosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylateSTEP A: Dimethylethyl 1R-[1α-, 3α-(R+S)]3-[2,2,2-trichloro-1-(diethoxyphosphoryloxy)-ethyl]2,2-dimethyl-cyclopropane carboxylate

0.84 ml of chloroform and 1.21 g of potassium tertbutylate in 10 ml oftetrahydrofuran were added at -60° C. to a solution of 1.98 g of1,1-dimethylethyl 2,2-dimethyl-3-keto-(1α, 3α-)-cyclopropane carboxylatein 10 ml of tetrahydrofuran and the mixture was stirred for 30 minutesat -60° C. and 1.88 g of 0,0-diethyl-chlorothiophosphate were added andthe temperature was allowed to return to 20° to 25° C. Stirring wascontinued for 5 hours and the reaction mixture was poured into a normalsolution of hydrochloric acid, and extracted with ether. The extractswere separated and evaporated to dryness under reduced pressure, thenchromatographed over silica and eluted with a hexane-isopropyl ethermixture (9-1) to obtain 2.15 g of dimethylethyl 1R-[1α-, 3α-(R+S)]3,-[2,2,2-trichloro-1-(diethoxythiophosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate.

STEP B: 1R-[1α-, 3α-(R+S)]3-[2,2,2-trichloro-1-(diethoxythiophosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylic acid

Using the procedure of Step B of the previous Example, the product ofStep A was reacted to obtain 1R-[1α-, 3α-(R+S)]3-[2,2,2-trichloro-1-(diethoxythiophosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylic acid.

STEP C: α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R or S)]3-[2,2,2-trichloro-1-diethoxythiophosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate

Using the procedure of Step C of the previous Example, the product ofStep B was reacted and the product obtained was chromatographed oversilica and eluted with a hexane-ethyl acetate mixture (7-3) to obtain0.850 g of isomer A of α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R or S)]3-[2,2,2-trichloro-1-diethoxythiophosphoryloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate.

NMR Spectrum

Paired CH₃ 73-4 HZ

H cyclopropyl 110 to 116 Hz

CH--O--P 312 to 342 Hz

CH-- 402

Aromatics 416 to 457 and 0.800 g of product B.

NMR Spectrum

Paired CH₃ 73-75 Hz --CH-- 384 HZ

Aromatic 425 or 452 Hz --CN

EXAMPLE 15 α-Cyano-3-phenoxy-benzyl 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate STEP A: Dimethylethyl 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-hydroxyethyl]-2,2-dimethyl-cyclopropane carboxylate

With stirring under a nitrogen atmosphere, 2.2 ml of chloroform, then2.95 g of potassium tertbutylene and 25 ml of tetrahydrofuran were addedat -60° to -55° C. to a mixture of 4.95 g of tertbutyl 3-formyl-1R, 3R2,2-dimethyl-cyclopropane carboxylate and 50 ml of tetrahydrofuran andthe reaction mixture was stirred for 2 hours and 30 minutes. Extractionwas carried out with ether and the organic phase was washed, dried andevaporated to dryness under reduced pressure. The product obtained waschromatographed by eluting with a hexane-ethyl acetate mixture (7-1) toobtain 6.45 of dimethyl ethyl 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-hydroxy-ethyl]-2,2-dimethyl-cyclopropanecarboxylate melting at 50° C.

STEP B: Dimethylethyl 1R-[1α-, 3α-(R)] 3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-cyclopropane carboxylate

5.6 ml of triethylamine and 6 ml of tetrahydrofuran were added at 0° to5° C. to a mixture of 6.35 g of the product of Step A, 65 ml oftetrahydrofuran and 3.2 ml of mesyl chloride and the reaction mixturewas poured into water and extracted with ether. The extracts were driedon sodium sulfate, filtered and evaporated to dryness to obtain 8.1 g ofdimethylethyl 1R-[1α-, 3α-(R)] 3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-cyclopropane carboxylate melting at 106° C.

STEP C: 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-methysulfonyloxyethyl]-cyclopropane carboxylic acid

6.5 g of the product of Step B, 65 ml of benzene and 150 mg of p-toluenesulfonic acid were refluxed for 1 hour and the reaction mixture waspoured into water, extracted with methylene chloride and brought todryness to obtain 5.15 g of crystals of 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-cyclopropane carboxylicacid melting at 148° C.

STEP D: α-Cyano-3-phenoxy-benzyl 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate

Using the procedure of Example 1, esterifying the acid obtained in theprevious Step with (S)α-cyano 3-phenoxy-benzyl alcohol yieldedα-cyano-3-phenoxy-benzyl 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate with a specific rotation of [α]_(D) ²⁰ =+33°±1° (c=1% inCHCl₃).

EXAMPLE 16 (S)α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate

The product was prepared by esterification of the acid of Step C ofExample 15 with S α-cyano-4-fluoro-3-phenoxy-benzyl alcohol and it had aspecific rotation of [α]_(D) ²⁰ =+38°±1° (c=1.5% in CHCl₃)

EXAMPLE 17 α-Cyano 1-(6-phenoxy-2-pyridyl)-methyl 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-methysulfonyloxyethyl]-2,2-dimethyl-cyclopropanecarboxylate

The product was prepared by esterification of the acid of Step C ofExample 15 with RS-cyano-1-(6-phenoxy-2-pyridyl)-methyl alcohol and ithad a specific rotation of [α]_(D) ²⁰ =2°±1° (c=0.8% in CHCl₃).

EXAMPLE 18 2-Methyl-3-phenyl-benzyl 1R-[1α-, 3α-(R)]3-[2,2,2-trichloro-1-methylsulfonyloxyethyl]-cyclopropane carboxylate

The product was prepared by esterification of the acid of Step C ofExample 15 with 2-methyl-3-phenyl-benzyl alcohol and it had a specificrotation of [α]_(D) ²⁰ =20°±1° (c=1% in CHCl₃)

EXAMPLE 19 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S*) 3α-(R*)] 2,2-dimethyl3-[2,2,2-trichloro-1-(4-methylphenylsulfonyloxyethyl)]-cyclopropanecarboxylate STEP A: Dimethylethyl 1R-[1α, 3α(R*)]3-[2,2,2-trichloro-1-(4-methylphenylsulfonyloxy)]-ethyl-2,2-dimethyl-cyclopropanecarboxylate

1.7 ml of chloroform and then 2.42 g of potassium tertbutylate and 20 mlof tetrahydrofuran were added at -60° C. to a suspension of 3.96 g oftertbutyl (1R,3R) 3-formyl-cyclopropane carboxylate and 20 ml oftetrahydrofuran and stirring was carried out for 30 minutes at -60° C. 4g of tosyl chloride and 10 ml of tetrahydrofuran were added over 15minutes at -60° C. and the mixture was stirred for 30 minutes at -60° C.and then poured into 200 ml of a normal solution of hydrochloric acid.Extraction was carried out with ether and the extracts were washed,separated and evaporated to dryness under reduced pressure to obtain 5.3g of dimethylethyl 1R-[1α,3α(R*)]3-[2,2,2-trichloro-1-(4-methylphenylsulfonyloxy)]-ethyl-2,2-dimethyl-cyclopropanecarboxylate.

STEP B: 1R-[1α, 3α-(R*)] 3-[2,2,2-trichloro-1-(4-methylphenylsulfonyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylic acid

The ester of Step A was refluxed in benzene in the presence of p-toluenesulfonic acid to obtain 1R-[1α, 3α-(R*)]3-[2,2,2-trichloro-1-(4-methylphenylsulfonyloxy)-ethyl]-2,2-dimethyl-cyclopropanecarboxylic acid melting at 190° C.

STEP C: α-Cyano-3-phenoxy-benzyl 1R-[1α-(S*) 3α-(R*)]2,2-dimethyl-3-[2,2,2-trichloro-1-(4-methylphenylsulfonyloxy)-ethyl]-cyclopropanecarboxylate

Esterification of the acid of Step B with S α-cyano-3-phenoxybenzylalcohol was carried out with procedure of Step C of Example 1 to obtainα-cyano-3-phenoxy-benzyl 1R-[1α-(S*) 3α-(R*)]2,2-dimethyl-3-[2,2,2-trichloro-1-(4-methylphenylsulfonyloxy)-ethyl]-cyclopropanecarboxylate with a specific rotation of [α]_(D) ²⁰ =77.5°±1.5° (c=1.1%in CHCl₃).

EXAMPLE 20 α-Cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(S)] 2,2-dimethyl3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropane carboxylateSTEP A: 1,1-dimethylethyl 1R-[1α, 3α-(S)] 2,2-dimethyl3-[2,2,2-tribromo-1-hydroxyethyl]-cyclopropane carboxylate

26 ml of bromoform were added to 39.6 g of 1,1-dimethylethyl 1R, 3R,2,2-dimethyl-3-keto-cyclopropane carboxylate in solution in 200 ml oftetrahydrofuran and 17.5 g of potassium methylate, 100 ml oftertbutanol, 60 ml of tetrahydrofuran and 60 ml of dimethylformamidewere added to the solution. The mixture was stirred for one hour at -10°C., then for one hour at +10° C. and then poured into water. Extractionwas carried out with isopropyl ether and the extracts were dried andevaporated to dryness, under vacuum. The two diastereoisomers obtainedwere separated by chromatography

STEP B: 1,1-dimethylethyl 1R-[1α, 3α-(S)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

A mixture of 4 g of the product of Step A, 40 ml of tetrahydrofuran and2.03 g of mesyl chloride was cooled to 0°±5° C. and 1.78 g oftriethylamine and 5 ml of tetrahydrofuran were added at 0°±5° C. Themixture was stirred for 2 hours at 0°±5° C. and then was poured intowater, and extracted with methylene chloride. The extracts were driedand evaporated to dryness under reduced pressure and the residue waspurified by crystallization from hexane, then from isopropyl ether toobtain 2.9 g of 1,1-dimethylethyl 1R-[1α, 3α-(S)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate melting at 159° C.

STEP C: 1R-[1α, 3α-(S)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylic acid

A mixture of 2.3 g of the product of Step B and 25 ml of benzene wasrefluxed and 70 mg of toluene sulfonic acid were added. The mixture wascooled, washed with water, dried and evaporated to dryness under reducedpressure to obtain 1.8 g of 1R-[1α, 3α-(S)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylic acid melting at 168° C.

STEP D: α-Cyano-3-phenoxy-benzyl 1R-[1α(S)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

0.78 g of dicyclohexylcarbodiimide and 3 ml of methylene chloride wereadded to a solution of 1.8 g of the product of Step C, 20 ml ofmethylene chloride, 0.86 g of (S) α-cyano-3-phenoxy-benzyl alcohol and0.1 g of 4-dimethylamino-pyridine. The mixture was stirred at 20° to 25°C. for 2 hours and the product formed was dried and the filtrate wasevaporated to dryness under reduced pressure. A chromatography wascarried out with elution with a hexane-ethyl acetate mixture (7-3) toobtain 2 g of α-cyano-3-phenoxy-benzyl 1R-[1α(S) 3α (S)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate with a specific rotation [α]_(D) ²⁰ =1°±1° (c=1% in CHCl₃).

EXAMPLE 21 α-Cyano-3-phenoxy-benzyl [1R-[1α-S*, 3α-RS*,RS*]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate STEP A: 1,1-dimethylethyl[1R-[1α, 3α-(RS*, RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-hydroxyethyl]-cyclopropanecarboxylate

3.1 g of potassium tertbutylate in 20 ml of THF were slowly added at-70° C. to a solution of 5 g of 1,1-dimethylethyl 1R,cis2,2-dimethyl-3-formyl-cyclopropane carboxylate in 50 ml of THF and 3 mlof halothene (CF₃ CHClBr). After a sufficient contact at thistemperature, the medium was poured into a PO₄ H₂ Na aqueous solution andextraction was carried out with methylene chloride. The extracts werewashed with water, and with a saturated solution of sodium chloride,dried and evaporated to dryness under reduced pressure. The product waschromatographed on silica and eluted with a hexane-isopropyl ethermixture (8-2) to obtain 6.83 g of 1,1-dimethylethyl[1R-[1α, 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-hydroxyethyl]-cyclopropanecarboxylate.

STEP B: 1,1-dimethylethyl [1R-[1α-, 3α-(RS*RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropane carboxylate

8 ml of triethylamine were added at -10° C. to a mixture of 6.74 g ofthe product of Step A, 40 ml of methylene chloride and 4.3 ml of mesylchloride were added with stirring for one hour on an ice bath. Afterdecanting, the organic phase was washed with water and with a saturatedsolution of sodium chloride, dried and evaporated to dryness underreduced pressure to obtain 9 g of product which was chromatographed onsilica and eluted with a hexane-isopropyl ether mixture (8-2) to obtain5.67 g of 1,1-dimethylethyl [1R-[1α-, 3α-(RS*RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate melting at 100° C.

STEP C: [1R-[1α-, 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonylethyl]-cyclopropanecarboxylic acid

30 mg of p-toluene sulfonic acid were added at 40° C. to a solution of 1g of the product of Step B and 10 ml of methylene chloride and thereaction mixture was heated for 5 hours at 40° C., then poured on toice, and decanted. The organic phase was washed with water, dried onsodium sulfate and evaporated to dryness under reduced pressure toobtain 860 mg of [1R-[1α-, 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonylethyl]-cyclopropanecarboxylic acid melting at 138° C.

STEP D: (S) α-Cyano-3-phenoxy-benzyl [1R-[1α-(S*) 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

Esterification of the acid of Step C with S α-cyano-3-phenoxybenzylalcohol using the procedure of Step B of Example 1 yielded (S)α-cyano-3-phenoxy-benzyl [1R-[1α-(S*) 3α-(RS*, RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate.

NMR Spectrum (CDCl₃)

Paired methyls=1.24-1.27 ppm and 1.22-1.27 ppm

H₁ and H₃ =1.88 to 2.03 ppm

Ha=5.54 to 5.60 ppm

Hg=6.62 to 6.64 ppm

Aromatic H=6.99 to 7.42 ppm

EXAMPLE 22 α-Cyano-3-phenoxy-4-fluoro-benzyl [1R-[1α-(S*) 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropane-carboxylate

Using the procedure of Example 21, S α-cyano-4-fluoro-3-phenoxybenzylalcohol and the appropriate acid were reacted to obtainα-cyano-3-phenoxy-4-fluoro-benzyl [1R-[1α-(S*) 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate.

NMR Spectrum (CDCl₃)

Paired CH₃ =1.23-1.25 ppm.

H₁ H₃ =1.9-2.15 ppm.

SO₂ CH₃ =3.1 ppm.

H₁ '=5.32-5.7 ppm.

Benzyl H=6.5 ppm.

Aromatic H=6.85 to 7.6 ppm.

EXAMPLE 23 α-Cyano-3-phenoxy 2-pyridyl-methyl [1R-[1α-(R,S*) 3α-(RS*)]]2,2-dimethyl-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxy-ethyl]-cyclopropanecarboxylate

Using the procedure of Example 21, RS α-cyano1-(6-phenoxy-2-pyridyl-methyl alcohol and the acid were reacted toobtain α-cyano-3-phenoxy 2-pyridyl-methyl [1R-[1α-(R,S*) 3α-(RS*)]]2,2-dimethyl-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxy-ethyl]-cyclopropanecarboxylate

NMR Spectrum CDCl₃

CH₃ methyl=1.25 1.3 1.43 ppm

H₁ H₃ =1.93 2.03 ppm

SO₃ CH₃ =3.05-3.07 3.12-3.16 ppm

H_(1') =5.32-5.7 ppm

Benzyl H=6.36-6.55 ppm

Aromatic H=6.87-7.99 ppm

EXAMPLE 24 Pentafluoro-benzyl [1R-[1α-, 3α-RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropane carboxylate

Using the procedure of Example 21, pentafluorobenzyl alcohol was reactedto obtain pentafluoro-benzyl [1R-[1α-,3α- RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropane carboxylate melting at 101° C.

NMR Spectrum CDCl₃

Paired CH₃ =1.26-1.39 ppm

H₁, H₃ =1.75-1.98 ppm

SO₃ CH₃ =3.12-3.15 ppm

CO₂ --CH₂ =5.27 ppm

Ha=5.7 ppm

EXAMPLE 25 2-methyl-3-phenyl-benzyl [1R-[1α-, 3α-(RS,RS)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

Using the procedure of Example 21, 2-methyl-3-phenyl-benzyl alcohol wasreacted to obtain 2-methyl-3-phenyl-benzyl [1R-[1α-, 3α-(RS, RS)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

NMR Spectrum CDCl₃

Principal diastereoisomers (2/3)

Paired CH₃ =1.22-1.37 ppm

CH₃ =2.22 ppm

CO₂ CH₂ =5.27 ppm O₂ S CH₃ 3.04 ppm

Ha (5.6/5.64 ppm H₁ 1.8 to 2.06 ppm (5.7 ppm H₃

Aromatic H=6.92/7.35 ppm

EXAMPLE 26 3-phenoxy-benzyl [1R-[1α-, 3α-RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxymethyl]-cyclopropanecarboxylate STEP A: 3-phenoxy-benzyl [1R-[1α-, 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-chloro-2-bromo-1-hydroxyethyl]-cyclopropanecarboxylate.

Using the procedure of Step A of Example 21, 3-phenoxy-benzyl 1R, cis2,2-dimethyl-3-formyl-cyclopropane carboxylate was reacted to obtain3-phenoxy-benzyl [1R-[1α-, 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-chloro-2-bromo-1-hydroxyethyl]-cyclopropanecarboxylate.

NMR Spectrum CDCl₃

Paired CH₃ =1.21 ppm

H₁ H₃ =1.54 to 1.92 ppm

H_(1') =4.28 ppm

CH₂ =5.08 ppm

O H=3.22 ppm

STEP B: 3-phenoxy-benzyl [1R-[1α-, 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate

Mesylation was carried out under the conditions of Step B of Example 21to obtain 3-phenoxy-benzyl [1R-[1α-, 3α-(RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate.

NMR Spectrum CDCl₃

Paired CH₃ =1.23/1.36 ppm

H₁ H₃ =1.8 to 2.06 ppm

CH₃ SO₂ =3.08/3.11 ppm

CO₂ CH₂ =5.15 ppm

H_(1') =3.85 ppm to 5.78 ppm

Aromatic H's, 6.87 to 7.55 ppm

EXAMPLE 27 [1R-[1α-, 3α-]]2,2-dimethyl-3-[2-trifluoromethyl-2-chloro-ethenyl]-cyclopropanecarboxylic acid

2 g of 3-phenoxy-benzyl [1R-[1α-, 3α- (RS*,RS*)]]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate were hydrogenated in 30 ml of ethanol in the presence of 200mg of 10% palladium catalyst and filtration was carried out. Thefiltrate was evaporated to dryness under reduced pressure to obtain aresidue which was dissolved in 20 ml of a normal sodium hydroxidesolution. The aqueous phase was washed with methylene chloride,acidified with concentrated hydrochloric acid and extracted withmethylene chloride. The extracts were dried and evaporated to dryness toobtain 400 mg of [1R-[1α-, 3α-]]2,2-dimethyl-3-[2-trifluoromethyl-2-chloro-ethenyl]-cyclopropanecarboxylic acid melting at 103° C.

    ______________________________________                                        NMR Spectrum CDCl.sub.3                                                       ______________________________________                                        Isomer Z Ha     = 6.83  6.98       ppm                                        Isomer DE       = 6.55  6.7        ppm                                        ______________________________________                                    

EXAMPLE 28 [2-methyl-(1,1'-biphenyl)-3-yl]-methyl 1R-[1α,3α-(RS*,RS*)]2,2-dimethyl-3-[2-bromo-2-chloro-1-[4-methylphenylsulfonyloxy]-3,3,3-trifluoropropyl-cyclopropanecarboxylate STEP A: [2-methyl-(1,1'-biphenyl)-3-yl]-methyl 1R(1α,3α)-2,2-dimethyl-3-formyl-cyclopropane carboxylate

0.55 g of sodium hydride were added slowly at 0° to 5° C. to a solutionof 3.5 g of 1R (1α,3α) 2,2-dimethyl-3-formyl carboxylic acid in 100 mlof THF and after stirring for one hour at 0° C., 12.9 g of[2-methyl-(1,1'-biphenyl)-3-yl]-methyl bromide in 30 ml ofdimethylformamide were added. Stirring was maintained for 22 hours atambient temperature and part of the solvent was evaporated. The mixturewas poured on to iced water and extracted with isopropyl ether. Theorganic phase was dried, evaporated to dryness and the residue waschromatographed on silica. (Eluent: hexane-isopropyl ether 7-3) toobtain 7.7 g of [2-methyl-(1,1'-biphenyl)-3-yl]-methyl 1R(1α,3α)-2,2-dimethyl-3-formyl-cyclopropane carboxylate.

STEP B: [2-methyl-(1,1'-biphenyl)-3-yl]-methyl 1R-[1α,3α-(RS*,RS*)]2,2-dimethyl-3-[2-bromo-2-chloro-1-[4-methylphenylsulfonyloxy]-3,3,3-trifluoropropyl-cyclopropanecarboxylate

1.3 g of potassium tertbutylate dissolved in 10 ml of tetrahydrofuranwere slowly added at -60° C. to 3.22 g of the product of Step A and 1.6ml of halothane (CF₃ CHBrCl) in solution in 15 ml of tetrahydrofuran.Then still at -60° C., 3.8 g of tosyl chloride and 0.8 g of4-dimethylamino-pyridine in 20 ml of tetrahydrofuran were added. After90 minutes of contact at -60° C., the reaction medium was poured into asolution of potassium mono phosphate and after extraction with methylenechloride, washing with water and drying of the organic phase andchromatography of the dry residue on silica (eluent: hexane-isopropylether 8-2), 3.5 g of pure [2-methyl-(1,1'-biphenyl)-3-yl]-methyl1R[1,3-(RS*,RS*)]2,2-dimethyl-3-[2-bromo-2-chloro-1-[4-methylphenylsulfonyloxy]-3,3,3-trifluoropropyl-cyclopropanecarboxylate acid were isolated.

NMR Spectrum (CDCl₃)

Paired CH₃ =1.24-1.38 ppm

tosyl CH₃ =2.4 ppm

CH₃ =2.25 ppm

H₁ H₃ =1.83 to 2.1 ppm

H_(1') =5.73-5.9 ppm

EXAMPLE 29 α-Cyano-3-phenoxy-benzyl [1R-[1α-,3α-(RS*,RS*)]]3-[2-bromo-2-chloro-1-[diethoxyphosphonyloxy)]-3,3,3-trifluoropropyl-2,2-dimethyl-cyclopropanecarboxylate STEP A: 1,1-dimethylethyl 1R (1α,3α-(RS*,RS*)3-(2-bromo-2-chloro-1-[diethoxyphosphonyloxy)]-3,3,3-trifluoropropyl)-2,2-dimethyl-cyclopropanecarboxylate

1.3 g of potassium tertbutylate dissolved in 10 ml of tetrahydrofuranwere added slowly at -60° C. to a solution of 2 g of 1,1-dimethylethyl1R (1α,3α-) 3-formyl-2,2-dimethyl-cyclopropane carboxylate and 1.2 ml ofhalothane (CF₃ CHBrCl) in 20 ml of tetrahydrofuran. After stirring for15 minutes at -60° C., a solution of 1.6 ml of diethyl phosphatechloride in 4 ml of tetrahydrofuran was added dropwise. After 30 minutesof contact at -60° C., the mixture was poured into an aqueous solutionof potassium mono phosphate. Extraction with methylene chloride yieldedan oil which was purified by chromatography on silica to obtain 2.1 g of1,1-dimethylethyl 1R (1α-,3α-(RS*,RS*)3-(2-bromo-2-chloro-1-[diethoxyphosphoryloxy]-3,3,3-trifluoropropyl)-2,2-dimethyl-cyclopropanecarboxylate.

STEP B: α-Cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α-(RS*,RS*)]3-(2-bromo-2-chloro-1-diethoxyphosphonyloxy3,3,3-trifluoropropyl)-2,2-dimethyl-cyclopropane carboxylate

1.74 g of the product of Step A were heated for 48 hours at reflux of 15ml of benzene in the presence of 60 mg of p-toluene sulfonic acid. Thereaction mixture was poured into a mixture of water and ice andextracted with methylene chloride. The extracts were washed, dried andconcentrated to dryness. The residue was chromatographed over silica(eluent: hexane-ethyl acetate 1-1) and the intermediate acid wasobtained. All of the acid was esterified with 0.46 g of Sα-cyano-3-phenoxybenzyl alcohol made the conditions of Step B ofExample 1. The purification by chromatography provided 0.6 g ofα-cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α-(RS*,RS*)]3-(2-bromo-2-chloro-1-diethoxyphosphoryloxy3,3,3-trifluoropropyl)-2,2-dimethyl-cyclopropane carboxylate.

NMR Spectrum (CDCl₃)

Paired CH₃ =1.17-1.23 ppm

CH₃ of EtO=1.36 ppm

CH₂ of EtO=4.17 ppm

H₁ -H₃ =1.93-1.96 ppm

H_(1') =5.21 ppm

Benzyl H=6.55 ppm

EXAMPLE 30 α-Cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α- (R)]2,2-dimethyl-3-[2,2,2-tribromo-1-[(3-hydroxy-2-methyl)-propylsulfonyloxy)-ethyl]-cyclopropanecarboxylate

5 g of the product of Example 5 and 3.75 g of N-methylmorpholine-N-oxidein 125 ml of tetrahydrofuran and 40 ml of water were mixed together atambient temperature. 100 mg of osmium tetroxide were added, and stirringwas carried out for 22 hours at 20° C. The reaction medium was dilutedwith 250 ml of methylene chloride, cooled to 0° C. and then 6 g ofsodium hydrosulfite in solution in 40 ml of water were added slowly. Themixture was allowed to return to ambient temperature, dried, and thesolvents were eliminated under reduced pressure to obtain 5.1 g of crudeproduct which was chromatographed on silica (eluent: hexane-ethylacetate 85-15) to obtain 1.7 g of α-cyano-3-phenoxy-benzyl 1R-[1α- (S)3α- (R)]2,2-dimethyl-3-[2,2,2-tribromo-1-[(3-hydroxy-2-methyl)-propylsulfonyloxy)-ethyl]-cyclopropanecarboxylate. Then after treatment with ether, 1.4 g of amorphous productwith a specific rotation of [α]_(D) ²⁰ =+38°±1° (c=1.% in chloroform)were obtained.

    ______________________________________                                        Analysis: C.sub.26 H.sub.28 Br.sub.3 NO.sub.8 S: molecular weight =           754.306                                                                       ______________________________________                                        Calcu-                                                                              % C 41.40 % H 3.74 % N 1.86                                                                             % Br 31.78                                                                            % S 4.25                              lated:                                                                        Found:                                                                              41.7      3.7      1.9    30.0    4.1                                   ______________________________________                                    

EXAMPLE 31 α-Cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-[(3-hydroxy-2-hydroxy)-propylsulfonyloxy)-ethyl]-cyclopropanecarboxylate

Using the procedure of Example 30, the product of Example 9 was reactedto obtain after chromatography on silica (eluent: methylenechloride-ethyl acetate 1-1) and taking up the residue in ether, 2.6 g ofα-cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α- (R)]2,2-dimethyl-3-[2,2,2-tribromo-1-[(3-hydroxy-2-hydroxy)-propylsulfonyloxy)-ethyl]-cyclopropanecarboxylate with a specific rotation of [α]_(D) ²⁰ =+41°±1.5° (c=0.7% inCHCl₃).

    ______________________________________                                        Analysis: C.sub.25 H.sub.26 Br.sub.3 NO.sub.8 S: molecular weight =           754.306                                                                       ______________________________________                                        Calcu-                                                                              % C 40.56 % H 3.54 % N 1.89                                                                             % Br 32.38                                                                            % S 4.33                              lated:                                                                        Found:                                                                              40.8      3.3      1.8    30.5    4.3                                   ______________________________________                                    

EXAMPLE 32 α-Cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-[(2,2-dimethyl-3-dioxolan-4-yl)-methylsulfonyloxy)-ethyl]-cyclopropanecarboxylate

1.3 g of the product of Example 31 and 130 mg of p-toluene sulfonic acidwere stirred for 2 hours at 20° C. in 130 ml of acetone and then wasdiluted with 100 ml of water. After drying, the solvents were eliminatedunder reduced pressure to obtain 1.25 g of residue which waschromatographed over silica (eluent: hexane-ethyl acetate 3-1) to obtain1.15 g of α-cyano-3-phenoxy-benzyl 1R-[1α- (S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-[(2,2-dimethyl-3-dioxolan-4-yl)-methylsulfonyloxy)-ethyl]-cyclopropanecarboxylate with a specific rotation of [α]_(D) ²⁰ =+44°±1.5° (c=1% inCHCl₃).

Using the procedure of the previous Examples, the following productswere prepared:

EXAMPLE 33

(S) α-cyano-3-phenoxy-benzyl (1R,cis)2,2-dimethyl-3-(2,2,2-tribromo-1-trimethylsilyloxyethyl)-cyclopropanecarboxylate melting at 98° C. and having a specific rotation of [α]_(D)²⁰ =+64°±1° (c=2% in toluene).

EXAMPLE 34

α-Cyano-3-phenoxy-benzyl [1α- (S), 3α- (R)] 3-[2,2,2-tribromo-1-(2-ethylpyridinium-phosphate)-ethyl]-2,2-dimethyl-cyclopropane carboxylate witha specific rotation of [α]_(D) ²⁰ =+13°±2° (c=0.65% in chloroform).

EXAMPLE 35

α-Cyano-3-phenoxy-benzyl [1α- (S), 3α-(R)] 3-[2,2,2-tribromo-1-(2-ethyltrimethylammonium phosphate)-ethyl]-2,2-dimethyl-cyclopropanecarboxylate with a specific rotation of [α]_(D) ²⁰ =+14°±1° (c=1% inchloroform).

EXAMPLE 36

3-phenoxy-benzyl (1R,cis)2,2-dimethyl-3-(2,2,2-trichloro-1R-methoxyethyl)-cyclopropanecarboxylate

    ______________________________________                                        Analysis: C.sub.22 H.sub.23 Cl.sub.3 O.sub.4                                  ______________________________________                                        Calculated:                                                                              % C 57.72 % H 5.06   % Cl 23.23                                    Found:     57.8      5.1        23.0                                          ______________________________________                                    

EXAMPLE 37

(RS) α-cyano-3-phenoxy-benzyl (1R,cis)2,2-dimethyl-3-[2,2,2-trichloro-1R-methoxyethyl]-cyclopropanecarboxylate

    ______________________________________                                        Analysis: C.sub.23 H.sub.22 Cl.sub.3 NO.sub.4                                 ______________________________________                                        Calculated:                                                                            % C 57.22 % H 4.59  % Cl 22.03                                                                            % n 2.9                                  Found:   57.5      4.7       21.9    2.8                                      ______________________________________                                    

EXAMPLE 38

3-phenoxy-benzyl (1R,cis)2,2-dimethyl-3-[2,2,2-trichloro-1R-acetyloxyethyl]-cyclopropanecarboxylate

    ______________________________________                                        Analysis: C.sub.23 H.sub.23 Cl.sub.3 O.sub.5                                  ______________________________________                                        Calculated:                                                                              % C 56..87                                                                              % H 4.77   % Cl 21.89                                    Found:     56.9      4.8        1.7                                           ______________________________________                                    

EXAMPLE 39

(R) or (S) α-cyano-3-phenoxy-benzyl (1R,cis)2,2-dimethyl-3-[2,2,2-trichloro-1R-methanesulfonyloxyethyl]-cyclopropanecarboxylate with a specific rotation of [α]_(D) ²⁰ =+7° (c=0.75% inbenzene).

EXAMPLE 40 Preparation of a Soluble Concentrate

A homogeneous mixture was made of

    ______________________________________                                        Product of Example 2                                                                            0.25 g                                                      Piperonyl butoxide                                                                              1.00 g                                                      Tween 80          0.25 g                                                      Topanol A         0.1 g                                                       Water             98.4 g                                                      ______________________________________                                    

EXAMPLE 41 Preparation of an Emulsifiable Concentrate

The following are homogeneously mixed:

    ______________________________________                                        Product of Example 3                                                                            0.015 g                                                     Piperonyl butoxide                                                                              0.5 g                                                       Topanol A         0.1 g                                                       Tween 80          3.5 g                                                       Xylene            95.885 g                                                    ______________________________________                                    

EXAMPLE 42 Preparation of an Emulsifiable Concentrate

A homogeneous mixture was made of:

    ______________________________________                                        Product of Example 8                                                                            1.5 g                                                       Tween 80          20.00 g                                                     Topanol A         0.1 g                                                       Xylene            78.4 g                                                      ______________________________________                                    

EXAMPLE 43 Preparation of a Fumigant Composition

The following were mixed homogeneously:

    ______________________________________                                        Product of Example 20                                                                           0.25 g                                                      Tabu powder       25.00 g                                                     Cedar leaf powder 40.00 g                                                     Pinewood dust     33.75 g                                                     Brilliant green   0.5 g                                                       p-nitrophenol     0.5 g                                                       ______________________________________                                    

EXAMPLE 44 Example of Alimentary Feed for Animals

A feed containing the following was used as a balanced basic food:maize, dehydrated alfafa, wheat straw, palmetto cobe with molasses,urea, a vitamin-containing mineral seasoning. This feed contained atleast 11% crude protein substances (of which 2.8% were contributed byurea), 2.5% fatty substances and at most 15% cellulose substances, 6%mineral substances and 13% humidity. The feed corresponded to 82 fodderunits per 100 kilos and contained per 100 kilos 910,000 I.U.s. ofvitamin A, 91,000 I.U.s of vitamin D₃, 150 mg of vitamin E, 150 mg ofvitamin C. 0.3 kg of the compound of Example 1 per 100 kg of total foodwere incorporated in this food.

EXAMPLE 45 Example of Feed for Animals

The same balanced basic feed was used as for Example 44 with 0.04 kg ofthe compound of Example 2 per 100 kg of total food incorporated intothis food.

BIOLOGICAL STUDY 1) Study of the Knock-Down Activity on the Domestic Fly

The insects tested were female domestic flies aged from 4 to 5 days andthe operation was carried out by topical spraying of 1 microliter ofacetone solution on the dorsal thorax of the insects by an Arnoldmicromanipulator. 50 flies were used per treatment and a mortality testwas carried out 24 hours after treatment. The results obtained expressedin LD₅₀ or dose in nanograms per individual necessary to kill 50% of theinsects are in the following Table.

    ______________________________________                                        Compound of    LD.sub.50 in                                                   Example        ng/insect                                                      ______________________________________                                         2             1.7                                                             3             2.7                                                             4             8.7                                                             8             1.3                                                            20             2.3                                                            21             1.1                                                            22             0.9                                                            30             5.7                                                            31             5.2                                                            32             4.5                                                            ______________________________________                                    

Conclusion

The products of the invention are endowed with a very good knock-downeffect on domestic flies.

2) Study of the Activity of Tarsal Contact on the Germanic Cockroach

The insects tested were male germanic cockroaches (Blatella germanica)and the test was carried out by depositing an acetone solution of knownconcentration on the bottom of a Petri dish with a diameter of 2 ml.After drying, 20 male cockroaches per concentration were allowed toremain for 1 hour and then the insects were transferred to a cleanmedium and their mortality was checked after 24 hours, 48 hours, 3 and 5days. The result expressed as a lethal concentration 50 (LC 50) in mg/m2are reported in the following Table.

    ______________________________________                                        Compound of    CL 50 in                                                       Example        mg/m2                                                          ______________________________________                                         2             1.2                                                             3             0.2                                                             4             2                                                               5             2.5                                                             8             0.07                                                            9             0.06                                                           20             0.3                                                            21             0.02                                                           22             0.005                                                          23             0.12                                                           25             0.15                                                           30             0.30                                                           31             0.29                                                           32             0.22                                                           ______________________________________                                    

3) Study of the Lethal Effect on Larvae of Spodoptera Littoralis

The tests were carried out by topical application of an acetone solutionon the dorsal thorax of the larvae by an Arnold micromanipulator 15larvae were used per dose of product tested and the larvae used werelarvae of the fourth larval stage, that is aged about 10 days when theywere bred at 20° C. and 65% relative humidity. After treatment, theindividual larva were placed on an artificial nutritive medium (Poitout,medium) and a mortality check was carried out 48 hours after treatment.The experimental results obtained are summarized in the following Table:

    ______________________________________                                        Study of the activity by topical application on                               larvae of Spodoptera littoralis                                               Test Results                                                                  Compound of    LD 50 in                                                       Example        ng/insect                                                      ______________________________________                                         2             13                                                              3             11                                                              4             25                                                              8             2.8                                                            20             6.5                                                            21             23.5                                                           22             9                                                              23             24                                                             25             32                                                             ______________________________________                                    

Various modifications of the products and methods of the invention maybe made without departing form the spirit or scope thereof and it shouldbe understood that the invention is intended to be limited only asdefined in the appended claims.

What we claim is:
 1. A compound of the formula ##STR41## wherein X₁ andX₂ are individually halogen, R₁ is selected from the group consisting ofhalogen, alkyl of 1 to 8 carbon atoms, aryl of 6 to 14 carbon atomsunsubstituted or substituted with halogen, perfluoroalkyl of 1 to 8carbon atoms, --CN and ##STR42## R' is alkyl of 1 to 8 carbon atoms, Yis selected from the group consisting of ##STR43## Alk₂, Alk₃, Alk₂ ',and Alk₃ ', are alkyl of 1 to 8 carbon atoms unsubstituted orsubstituted with at least one member of the group consisting of alkyl of1 to 5 carbon atoms, halogen, --CF₃ and hydroxyl, ortogether with##STR44## form the rings ##STR45## wherein A is alkylene of 1 to 6carbon atoms unsubstituted or substituted with at least one member ofthe group consisting of 1 to 5 carbon atoms, halogen, --CF₃ andhydroxyl.
 2. A compound of claim 1 wherein X₁ and X₂ are individuallychlorine, bromine or iodine.
 3. A compound of claim 1 wherein X₁ and X₂are bromine.
 4. A compound of claim 1 wherein R₁ is bromine, fluorine orchlorine.
 5. A compound of claim 1 wherein R₁ is --CF₃.
 6. A compound ofclaim 1 wherein R is selected from the group consisting of ##STR46##wherein W is hydrogen, methyl or methoxy.
 7. A compound of claim 1selected from the group consisting of α-cyano-3-phenoxy-benzyl1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-(methylsulfonyloxyethyl)-2,2,2-tribromoethyl]-cyclopropanecarboxylate α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, [2-methyl-3-phenyl-benzyl] 1R-[1α,3α-(RS,RS)]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate and α-cyano-3-phenoxy-benzyl 1R-[1α-,3α-(RS*,RS*)]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methysulfonyloxyethyl]-cyclopropanecarboxylate.
 8. A compound of the formula ##STR47## wherein R, R₁, X₁and X₂ have the definitions of claim 1 with the proviso that X₁, X₂ andR₁ can not all be halogen.
 9. An insecticide composition comprising aninsecticidally effective amount of at least one compound of claim 1 andan inert carrier.
 10. An acaricidal composition comprising anacaricidally effective amount of at least one compound of claim 1 and aninert carrier.
 11. A nematocidal composition comprising a nematocidallyeffective amount of at least one compound of claim 1 and an inertcarrier.
 12. A composition of claim 9 wherein in the active compound X₁and X₂ are individually chlorine, bromine or iodine.
 13. A compositionof claim 9 wherein in the active compound X₁ and X₂ are bromine.
 14. Acomposition of claim 9 wherein in the active compound R₁ is bromine,fluorine or chlorine.
 15. A composition of claim 9 wherein in the activecompound R₁ is --CF₃.
 16. A composition of claim 9 wherein in the activecompound R is selected from the group consisting of ##STR48## wherein Wis hydrogen, methyl or methoxy.
 17. A composition of claim 9 wherein theactive compound is selected from the group consisting ofα-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-methylsulfonyloxyethyl)-2,2,2-tribromoethyl]-cyclopropanecarboxylate α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, and α-cyano-3-phenoxy-benzyl 1R-[1α-,3α-(RS*,RS*)]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methysulfonyloxyethyl]-cyclopropanecarboxylate.
 18. An insecticidal composition of claim 9 also containingat least one pyrethrinoid ester selected from the group consisting ofesters of allethrolones of 3,4,5,6-tetrahydrophthalimido methyl alcoholof 5-benzyl 3-furyl methyl alcohol, of 3-phenoxy-benzyl alcohol and ofα-cyano-3-phenoxy-benzyl alcohol with chrysanthemic acids, by the estersof 5-benzyl-3-furyl methyl alcohol with 2,2-dimethyl3-(2-oxo-3,4,5,6-tetrahydrothiophenylidenemethyl)-cyclopropane-1-carboxylic acids, by the esters of3-phenoxy-benzyl alcohol and of α-cyano 3-phenoxy-benzyl alcohols withthe 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acids,by esters of α-cyano-3-phenoxy-benzyl alcohols with2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-1-carboxylic acids, bythe esters of 3-phenoxy benzyl alcohol with 2-parachlorophenyl2-isopropyl-acetic acids, by esters of allethrolones, of3,4,5,6-tetrahydrophthalimido-methyl alcohol, of 5-benzyl-3-furylmethylalcohol, of 3-phenoxy-benzyl alcohol and of α-cyano-3-phenoxy-benzylalcohols with the 2,2-dimethyl3-(1,2,2,2-tetrahaloethylcyclopropane-1-carboxylic acids, in which"halo" represents a fluorine, chlorine or bromine atom, it beingunderstood that the acid and alcohol copulas of the pyrethrinoid estersabove can exist in all their possible stereoisomeric forms.
 19. Acomposition of claim 9 containing a pyrethrinoid synergist.
 20. A methodof combatting insects comprising contacting insects with aninsecticidally effective amount of at least one compound of claim
 1. 21.A method of claim 20 wherein in the active compound X₁ and X₂ areindividually chlorine, bromine or iodine.
 22. A method of claim 20wherein in the active compound X₁ and X₂ are bromine.
 23. A method ofclaim 20 wherein in the active compound R₁ is bromine, fluorine orchlorine.
 24. A method of claim 20 wherein in the active compound R₁ is--CF₃.
 25. A method of claim 20 wherein in the active compound R isselected from the group consisting of ##STR49## wherein W is hydrogen,methyl or methoxy.
 26. A method of claim 25 wherein the active compoundis selected from the group consisting of α-cyano-3-phenoxy-benzyl1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[1-(methylsulfonyloxyethyl)-2,2,2-tribromoethyl]-cyclopropanecarboxylate α-cyano-3-phenoxy-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, α-cyano-3-phenoxy-4-fluoro-benzyl 1R-[1α-(S) 3α-(R)]2,2-dimethyl-3-[2,2,2-tribromo-1-methylsulfonyloxyethyl]-cyclopropanecarboxylate, and α-cyano-3-phenoxy-benzyl 1R-[1α-,3α-(RS*,RS*)]2,2-dimethyl-3-[2-trifluoromethyl-2-bromo-2-chloro-1-methysulfonyloxyethyl]-cyclopropanecarboxylate.